540 INSTRUMENTATION: WATER AND WASTEWATER ANALYSIS
and its use. There must be no perturbation of the sample
composition or physical characteristics which will nullify
or seriously distort the analysis results and be detrimental
to the purposes of the analysis.
Preservation is a means of preventing decomposition
and change of various biological or chemical components in
the sample. Standard Methods provides a treatment for the
preservation of specific components in a variety of samples
where preservation is possible (see Table 1).^2
Sampling Considerations Two types of changes must be
considered in order to define and carry out a proper sam-
pling program, i.e., time-based changes in the source to be
sampled and in the sample taken from the source.
Time-based changes in the source may be short or long
term. The short-term changes taking place are indicative of
biological, chemical, and/or physical interactions in the time
span assigned to repetitive sampling. Long-term changes
in the sources are related to ecological trends. It is impor-
tant to be aware of each of these types of changes so that
sample storage changes are not mistaken for sample source
changes.
In order to obtain a legitimate sample of water or waste-
water for analysis one must understand the nature the sample
and its time-based changes. Once a sample taken from the
source it may begin to change for many reasons as discussed
in the previous section, IIA, 1. The sample must be represen-
tative of the sample source, that is it must have the same bio-
logical, chemical, and physical characteristics of the source
at the time the sample is taken. Therefore the sampling pro-
cedure must not cause a change in the sample relative to the
source if there is to be an accurate correspondence between
the sample analysis and the nature of the sample source at
the time the sample was taken.
To prevent confusing the two variables, ecological changes
in the source and interactions in the sample that can occur in
the same time span in a series of samples, preservation of
the samples is undertaken to deter changes after sampling.
However, preliminary sampling and testing may be necessary
to indicate the type of time-based changes occurring. Then a
reliable program can be established with some certainty.
Three kinds of sampling schemes are undertaken in
consideration of the sample source characteristics—grab,
composite and integrated samples.
A grab sample is one taken at a given time and place.
If the source doesn’t change greatly during a long passage
of time or within a large distance in all directions from
the sampling point, the grab sample is useful. The results
from grab samples are said to represent the source for the
given values of distance from sampling location and time.
However a time and place series of grab samples is needed
to establish the constancy of analytical values for different
times and distances from the original grab sampling point.
With that information the sampling frequencies and times
for a sampling program can be established. The sampling of
solids, such as, benthic muds and sludges, requires great care
in order to obtain truly representative samples.
A series of samples collected and blended to give a
time-averaged sample is known as a composite or time-
composite sample. In another procedure the volume of
each sample of the series collected is proportional to flow
of the sample source, namely the water body or waste
stream. The samples of various volumes are composited
to provide the final time-composite sample. This type of
sample gives an average value over a time period and saves
analysis time and cost. Sampling frequencies and the total
time span of the series depends on the source. Composite
sampling may be used for process streams to determine
the effect of unit processes or to monitor a plant outfall
for daily or shift changes. However, biological, chemical,
and physical parameters that changes on storage during
the sampling time period can’t be reliably determined in
time-composited samples and another sampling protocol is
needed (see Table 1).
At times, simultaneous samples are needed from various
locations within a given source, such as a river or lake. Grab
samples are then composited, usually based on volumes pro-
portional to flow, and are called integrated samples. These
samples are used to determine average composition or total
loading of the source which varies in composition in its
breadth and depth. The sampling program for such sources is
complex and requires careful consideration for each unique
source.
Water and Wastewater Parameters
A large number of water quality parameters are utilized in
the characterization, management and processing of water
and wastewater. Table 2 lists a number of these param-
eters separated into three categories—physical, chemical
and biological. It is obvious that only some parameters are
considered to be pollution factors because they indicate con-
ditions of water during processing or in the natural state.
The STORET system of the USEPA lists more than four
hundred parameters separated into six major groups and is
used for the analysis, collection, processing and reporting of
data.^3 Table 3 gives a sampling of groups of parameters in
this system. Not all of these parameters are used frequently,
since many are rather unique to particular waste effluents. In
actuality, a very small number are used in the analysis of a
particular sample.
Water quality parameters may be divided into two groups,
specific and non-specific water quality parameters. Specific
parameters refer to chemical entities of all types, e.g., ions,
elements, compounds, complexes, etc. For example, in
Table 2 some specific parameters are ammonia, all metals
listed, dissolved oxygen, nitrates, sulfates, and so forth. Non-
specific parameters are included in three categories and some
examples are as follows: chemical (hardness, alkalinity, acid-
ity, BOD [biochemical oxygen demand], TOC [total organic
carbon], COD [chemical oxygen demand], chlorine demand),
physical (salinity, density, electrical conductance, filterable
residue), and physiological (taste, odor, color, turbidity, sus-
pended matter). Many of these non-specific parameters are
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